JPH05301937A - Synthetic resin - Google Patents

Abstract

Synthetic resin, containing, as essential components, A) a crosslinkable binder from the group consisting of polymerisation, polyaddition or polycondensation products containing reactive centres in the form of hydroxyl, thio or primary or secondary amino groups, and B) a crosslinking agent based on at least one polyoxyalkylene polyisocyanate, and C) a crosslinking agent which is different from (B) and is based on gamma 1) a polyisocyanate which is different from (B) or gamma 2) an organic compound which reacts with free amino groups of component (A) at elevated temperature to form an amide, or gamma 3) an organic compound which reacts with hydroxyl groups of component (A) at elevated temperature with transesterification, or gamma 4) a phenolic Mannich base, or a mixture of two or more crosslinking agents ( gamma 1) to ( gamma 4). h

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic resin. The synthetic resin of the present invention comprises, as an essential component, A) a group of polymerization, polyaddition or polycondensation products having reactive centers in the form of hydroxyl groups, thio groups, primary or secondary amino groups. Crosslinkable binder, and B) a crosslinking agent containing polyoxyalkylene isocyanate as a main component, and C) γ ₁ ) _{one of} polyvalent isocyanates different from (B), or γ ₂ ) a component at high temperature (A) Organic compound that reacts by forming an amide with a free amino group, or γ ₃ ) Organic compound that reacts by transesterification with the hydroxyl group of component (A) at high temperature, or γ ₄ ) Phenolic Mannich base Or a mixture of two or more binders (γ ₁ ) to (γ ₄ ) as a main component, and one of binders different from (B).

The invention further relates to aqueous dispersions containing the abovementioned synthetic resins and their use in electrophoretic lacquer baths.

The cathodic electrophoretic lacquering method is applied more and more frequently for coating metal parts, especially in the automotive industry. In that case, a cathodically depositable synthetic resin is required, which at the same time provides good corrosion protection and at the same time is impact-resistant, for example when automobile lacquers are subjected to stone impacts, such as crushed stones and winter roads. What is required is something that will not be damaged by the impact from the crushed stone-salt mixture applied to the.

[0004]

EP 70550 describes an aqueous dispersion for cathodic electrodeposition lacquer coating, which is obtained by the reaction of an epoxy resin based on bisphenol A with a polyoxyalkylene polyamine. Synthetic resins are used as binders.

The previously known systems, however, do not meet all the requirements, ie at the same time good corrosion protection and all other good use properties, but also particularly good crush stone impact resistance.

[0006]

The object of the present invention is therefore to provide synthetic resins which are suitable as coating materials.
The synthetic resin must then exhibit not only high crushing stone impact resistance, but also very good corrosion resistance.

[0007]

Accordingly, the synthetic resin originally defined was correspondingly discovered.

Component A According to the invention, the synthetic resin contains a crosslinkable binder. The binder content is preferably 50-95% by weight.

Binders of the binder which come into consideration as component A are polymerizations, polycondensations or polyadditions which contain reactive centers in the form of hydroxyl groups, thio groups, primary or secondary amino groups. It is a product. On these reactive centers the binder can be rendered water dispersible, for example by protonation, or it can be crosslinked by reaction with components (B) and (C). The average molecular weight Mw of the substrate is generally 2
Between 00 and 5000, preferably between 250 and 3000, in which case the content of reactive centers is generally 1.5 to 3.0 equivalents per molecule, preferably 1.8 to 2.5 equivalents. .. Examples of suitable materials are polyesters, alkyd resins, polyethers, polyacrylates, polyurethanes and polyepoxides. These substrates can be further replaced with amines, alcohols, thiols or compounds thereof.

Suitable polyesters are those composed of aliphatic and / or aromatic dicarboxylic acids having 4 to 10 carbon atoms and polyhydric alcohols or thiols. Examples of those dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid,
Azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid or terephthalic acid or derivatives of these dicarboxylic acids. Among the polyhydric alcohols are aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propanediol,
Butanediol, hexanediol, neopentyl glycol and hydroxypivalic acid neopentyl glycol ester, and higher polyhydric alcohols such as trimethylolpropane, glycerin, erythritol, pentaerythritol, trimethylolbenzol or trishydroxyethyl isocyanurate. ..

Suitable alkyd resins are similarly constructed, but additionally contain one or several monocarboxylic acids, such as fatty acids. Also, an alkyd resin containing a glycidyl ester of a branched carboxylic acid can be used.

Aliphatic or arylaliphatic polyethers having reactive centers can likewise be used. As is more suitable for the purpose, they can be obtained by reacting dihydric and / or polyhydric alcohols with ethylene oxide and / or propylene oxide.

Polyacrylates belong to the class of polymerization products, but they are present at 5 to 50% by weight, preferably 10%.
-30% by weight of monomers containing hydroxyl groups or amino groups or mixtures of various such monomers with 50-95% by weight, preferably 70-90% by weight
Can be produced by copolymerization with other unsaturated monomers. Included in the first category of monomers are, for example, isopropylaminopropylmethacrylamide and α, β.
- hydroxy ethylenically unsaturated carboxylic acid - (C ₂ -
C ₄₎ - alkyl esters, such as 2-hydroxyethyl - and hydroxypropyl methacrylate, and butanediol - monomethacrylate and the like. Among the last-mentioned groups of monomers are vinyl aromatic compounds such as styrene and vinyltoluol, vinyl esters of carboxylic acids having 2 to 18 carbon atoms (for example vinyl acetate and vinyl propionate), Vinyl alcohols of monoalcohols having 1 to 18 carbon atoms (for example vinyl methyl ether and vinyl isobutyl ether), esters of C ₁ -C ₁₂ -monoalcohols of acrylic acid and methacrylic acid,
The corresponding maleic acid, fumaric acid and itaconic acid diesters, acrylic acid amides, acrylic acid nitriles and the corresponding methacrylic acid derivatives and mixtures of these monomers belong. Furthermore, acrylates having an epoxide group, such as glycidyl methacrylate, can be polymerized, and those polymers can be made into derivatives by reaction with amines.

As the polycondensation product, for example, a condensation product of polycarboxylic acid and polyamine can be used. The reaction products of dimerized or trimerized fatty acids with polyamines (eg ethylenediamine, 1,2- and 1,3-diaminopropane, diethylenetriamine, dipropylenetriamine, triethylenetetraamine) are reactive centers in which they are required. As long as it contains

Polyurethanes from aliphatic and / or aromatic diisocyanates and aliphatic diols have likewise proved suitable as long as they have the required reactive centers. Examples of diisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluylene diisocyanate, naphthylene diisocyanate and 4,4′-diphenylene ether diisocyanate. can give. Suitable diols are, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester. However, also higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, trimethylolbenzol and trishydroxyethyl isocyanurate are considered. Particularly preferred binders are those whose basic structure is based on epoxy resins.

Epoxy resins which are reaction products of polyhydric phenols with epihalogenhydrins, the molecular weight of which can be adjusted by the ratio of phenol to epihalogenhydrin, can be used. Examples of such polyphenols are resorcin, hydroquinone, 2,2'-di-
(4-hydroxyphenyl) propane (bisphenol A), p, p'-dihydroxybenzophenone, p,
p'-dihydroxydiphenyl, 1,1-di- (4-hydroxyphenyl) ethane, bis- (2-hydroxy-
Naphthyl) -methane, 1,5-dihydroxynaphthylene and novolak. Bisphenol A is particularly preferably used. A particularly preferred epihalogenhydrin is epichlorohydrin.

In addition to epoxy resins from polyhydric phenols and epihalogenhydrins, polyhydric alcohols (eg ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3
-Propanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
2,6-hexanetriol, glycerin or bis-
Polyglycidyl ethers of (4-hydroxycyclohexyl) -2,2-propane) can be used.

What is particularly preferred is that the epoxy resin, which is a diglycidyl ether of bisphenol A, is partially modified with a polyhydric phenol, especially bisphenol A.

According to the invention, the epoxy resin can be reacted with one amine or a mixture of different amines. The amines are alkyl amines,
Alkylalkanolamines, polyoxyalkylene polyamines and polyvalent polyolefin amines. Suitable products can be obtained, for example, by reaction with an excess of primary alkyldiamines whose alkyl residue can have from 2 to 20 carbon atoms. Among the primary alkyldiamines which come into consideration are ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, neopentanediamine and hexamethylenediamine, among others. Suitable secondary dialkyl monoamines are those whose alkyl residue has 1 to 20 carbon atoms, in which case dimethylamine and diethylamine are particularly preferred. Likewise suitable are alkylalkanolamines, the alkyl and alkanol residues of which can each have from 1 to 20 carbon atoms, in which case the chain length of said residues may be the same or else It may be different. Alkylalkanolamines include, for example, ethylethanolamine, methylisopropanolamine and especially methylethanolamine. Polyoxyalkylene polyamines which can be used are, for example, polyoxyethylene polyamines, polyoxypropylene polyamines and polyoxybutylene polyamines. The class of polyolefin polyamines includes butadiene-acrylonitrile copolymers having amine end groups.

The possibility of further modifying the epoxy resin is
It is to react it with a secondary amine containing a protected primary amino group. In this case, only the secondary amino groups react with the epoxy resin, whereas the protected primary amino groups can be liberated after the above reaction, for example by addition of water. The alkyl residue of these compounds generally has 1 to 20 carbon atoms. Examples of such amines are the diketimines of diethylenetriamine, the ketimines of aminoethylethanolamine, the ketimines of N-methyl-ethylenediamine and the ketimines of N-aminoethylpiperazine. A particularly preferred ketimine is methylisobutylketimine.

If desired, the amine-modified epoxy resin can be chain extended with dicarboxylic acids such as sebacic acid or dimer fatty acids. The simultaneous use of monocarboxylic acids such as stearic acid or fatty acids is likewise possible.

According to the invention, polyhydric phenols, in particular diglycidyl ethers based on bisphenol A and epichlorohydrin, are particularly preferred as binders. The average molecular weight Mw of these compounds is usually between 200 and 5000, and they contain an average of about 1.5 to 3.0 epoxide groups per molecule, which is about 50 to about the epoxide equivalent weight.
Equivalent to 1000. Preferred epoxide equivalent weight is 150
~ 1500, especially about 400-500. It has been found to be particularly advantageous to modify these epoxy resins with amines. Dimethylaminopropylamine and methylethanolamine are particularly suitable in that case.

Component B The synthetic resin according to the invention contains as component B 5 to 50% by weight, in particular 10 to 30% by weight, of a crosslinking agent based on polyoxyalkylene polyisocyanate.

To avoid premature crosslinking, polyoxyalkylene polyisocyanates containing polyoxyalkylene polyisocyanates in the highest possible proportion are particularly preferred. Correspondingly, polyoxyalkylene polyisocyanates of the general formula I below are particularly preferred.

[0025]

[Chemical 1] Wherein R ^{1 to} R ³ can be the same or different from each other and represent residues from the group of hydrogen and C ₁ -C ₆ alkyl. The parameter m is between 1 and 10, preferably 1 and 3
Between Chain length n is between 1 and 50, preferably 1 and 3
It is between 0. In most cases polyoxyalkylene polyisocyanates having an average molecular weight Mw between 450 and 2500 are particularly preferred, but also 400 and 300
Those with an average molecular weight between 0 may also be suitable. Polyoxyalkylene polyisocyanates with Mw outside the range of 200 to 3800 usually provide no benefit. Particularly preferred polyoxyalkylene polyisocyanates are polyoxyethylene polyisocyanates, polyoxypropylene polyisocyanates and polyoxybutylene polyisocyanates.

Polyoxyalkylene polyisocyanates can be prepared from the corresponding amines by reaction with phosgene according to methods known in the literature (for example:
Houben-Weyl, "Methods of Organic Chemistry," H. et al. H
agemann edited and published, E4 edition, page 741 and below,
Georg-Thieme-Verlag, Stutt
gart, 1983).

The isocyanate groups of the binder component (B) can be masked according to the invention by, for example, ketoxime and / or polyols (meaning polyhydric aliphatic alcohols and aromatic polyols).

The polyoxyalkylene polyisocyanate is then generally reacted with an amount of ketoxime such that the ratio of NCO equivalents to N-OH equivalents is 3 to 5: 1, preferably 2.5 to 1.5: 1. Be done. The remaining isocyanate groups are masked with polyols and / or reacted with secondary amines and / or alkanolamines.

In the reaction of the polyoxyalkylene polyisocyanate with the polyol, their amount is such that the ratio of NCO equivalent to OH equivalent is generally 1.1 to 1.8 to 1,
It is preferably chosen to be between 1.2 and 1.7 to 1. Equivalent ratios of less than 1.1: 1 usually lead to jellying of the compounds, thus leading to a too low viscosity result. NCO excess 1.8: 1
If larger, molecules will be produced that have a molecular weight that is too small for most applications. The remaining isocyanate groups react with secondary amines and / or alkanolamines in the second reaction stage.

Furthermore, the polyoxyalkylene isocyanate can be masked so that binders that act at different temperatures are formed. Thus, the isocyanate groups can be masked, for example, in part in the first reaction stage with alcohols such as dimethylaminopropanol and ethanol and in the second reaction stage with polyols having phenol end groups. These phenolic end groups can then be reacted with formaldehyde and secondary amines, resulting in a binder having an isocyanate function (relatively high temperature) and a transamination function (relatively low temperature). ..

Preferred ketoxime are dialkylketoxime whose alkyl residues may be the same or different from one another and have 1 to 6 carbon atoms, wherein the alkyl group is linear, branched or cyclic. Can be one. As examples, mention may be made of dimethylketoxime, methylethylketoxime, diethylketoxime, methylpropylketoxime, dipropylketoxime, methylbutylketoxime, dibutylketoxime, methylpentylketoxime and methylhexylketoxime. Methylisobutyl ketoxime is particularly preferably used.

Aliphatic diols are among the polyols that can be used as masking agents,
Examples are diethylene glycol, 1,4-butanediol, 1,5-pentanediol, polyethylene glycol and polypropylene glycol. Preference is given to aromatic polyols whose average molecular weight is between 200 and 5000, in particular between 200 and 2000 and on average have 2 or more hydrogen atoms per molecule. Reaction products of bisphenol A with epoxy resins, in which case epoxy resins based on bisphenol A and epihalohydrin are preferred, have been found to be particularly suitable.

Component C Component C is generally 5 to 50% by weight, preferably 10 to
The crosslinking agent according to the invention in 30% by weight in a synthetic resin can be a protected isocyanate crosslinking agent different from component (B), a transesterification type, an amide exchange type or an amine exchange type crosslinking agent. .. However, it is also possible to use mixtures of different crosslinking agents. The crosslinker (C) can be an independent component of the synthetic resin. The crosslinker molecules may, however, also be associated with the binder (A). This so-called self-crosslinking binder is cross-linked only by adjusting the appropriate conditions when first used.

Protected isocyanate cross-linking agents include, for example, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, trimerized hexamethylene diisocyanate and triphenylmethane triisocyanate. Be considered. Of which, toluylene diisocyanate, 4,
4'-Diphenylmethane diisocyanate and isophorone diisocyanate are particularly preferred. These can be masked with, for example, the polyol (see component (B)) described above.

The compound forming the amide exchange type cross-linking agent is a compound containing a free carboxyl group, on which a carbalkoxymethyl group can be added, particularly preferably a polyester resin. The carbalkoxymethyl ester reacts with the free primary and / or secondary amino groups of the binder to form an amide.

Binders having hydroxyl groups as reactive centers can be hardened, for example by transesterification crosslinking agents. This cross-linking agent can be produced, for example, by reacting an epoxy resin containing bisphenol A and epihalohydrin as main components with a dicarboxylic acid in the first reaction step. In the second reaction stage, the polyepoxide-dicarboxylic acid adduct is reacted with a glycolic acid ester such as, for example, glycolic acid methyl ester, or with a glycidyl ester of ethylene oxide such as ethylene oxide, propylene oxide or a branched aliphatic carboxylic acid, In particular, it is reacted with versic acid glycidyl ester.

Mannich bases, reaction products from phenols, formaldehyde and secondary amines, can likewise be used as crosslinker component (C). For the production of this amine exchange type cross-linking agent, a compound having an epoxide group such as polyoxypropylene diglycidyl ether is reacted with a polyhydric phenol such as bisphenol A, and then dimethylamine, diethylamine, A dialkylamine such as piperidine,
It is then reacted with formaldehyde or a compound that provides formaldehyde. Hydroxyl groups, thiol groups and / or amine groups can be additionally introduced into the above-mentioned cross-linking agents by corresponding reactions.

Component D Pigment preparations can be added to the synthetic resin if desired. Thus, the synthetic resin is preferably 0-3.
It is possible to include 0% by weight of one or several pigments and a pigment preparation consisting of a resin having surface activity, a so-called friction resin. Pigments that can be used include, for example, iron oxide and lead oxide, strontium carbonate, carbon black, titanium oxide, talc, barium sulfate, cadmium yellow,
Metallic pigments such as cadmium red, phthalocyanine blue or aluminum flakes.

The compounding resin must have a high pigment-carrying capacity and be compatible with the respective binder of the synthetic resin. Preferred friction resins are those containing diglycidyl ether based on bisphenol A and epichlorohydrin, and modified with amines, especially hexamethylenediamine.

Component E Furthermore, the synthetic resin according to the invention comprises one or several additives, preferably various fillers, antioxidants, UV absorbers, accelerators, defoamers, and other additives such as polyvinyl. It can include ethers. These materials are usually 0 to about 10% by weight of the synthetic resin, especially 0.5 to 5%.
Make up weight percent. Among the preferred fillers are titanium dioxide and barium titanate. Benzotriazole and anilide oxalic acid have been found to be particularly good UV absorbers. Butyl glycol and propylene glycol phenyl ether are examples of accelerators. Butin-
A fatty acid ester of 1,4-diol or a naphthenic mineral oil also has a defoaming action.

The individual components of the synthetic resin can always be dissolved in an organic solvent. Solvents of interest are aromatic hydrocarbons (eg toluol and xylol), glycols, glycol ethers (eg diethylene glycol methyl ether) and alcohols.

The synthetic resins according to the invention can serve as coating materials for various supports as a mixture of the components or their solutions.

Acids, particularly preferably carboxylic acids (for example:
The synthetic resin can be dispersed in water by the addition of formic acid, acetic acid, or lactic acid), but also an inorganic acid (eg phosphoric acid), and by customary methods supports made of wood, synthetic resin or metal. Painted on. However, particularly preferably, the components are each separately protonated, separately dispersed in water, the organic solvent is removed if desired, and then the individual dispersions are mixed. It is of course also possible to add the additives to the individual components in each case and then to disperse them.

The synthetic resins according to the invention in the form of their aqueous dispersions are suitable for electrophoretic lacquering of electrically conductive objects, for example metal parts. For cathodic electrophoretic coating, the electrophoretic bath generally has a solids content of 5 to 40% by weight, preferably 10%.
Adjusted to ~ 30% by weight. Deposition is typically 15-4
At a temperature of 0 ° C., preferably 20-35 ° C., for 1-5 minutes, and a pH value of 5-8, preferably at neutral point, 50
It is carried out at a voltage of ~ 500V, preferably 150-450V. The conductive object to be coated is then connected as a cathode. The deposited film cures at a temperature of about 100 ° C to about 200 ° C in about 10 to about 30 minutes.

The coatings obtained using the synthetic resins according to the invention show very good crush stone impact resistance and at the same time very good corrosion protection. In addition, it has long-term stable storage because the individual components are dispersed separately.

[0046]

EXAMPLES Abbreviations 1) BPA: Bisphenol A (p, p'-dihydroxyphenylpropane) 2) EEW: Epoxide equivalent 3) MiBK: Methyl isobutyl ketone 4) NCO-EW: Isocyanate equivalent 5) VE: Completely desorbed Salted

Synthetic resin 1 wt% equivalent component ──────────────────────────────────── (A) : Binder 1 ──────────────────────────────────── 50.4 3.74 BPA ¹⁾ as the main component Diglycidyl ether, EEW ²⁾ = 188 18.6 1.0 Polycaprolactone diol, Mw ~ 540 2.5 -Xylol 13.7 1.74 BPA 0.3 -Benzylmethylamine 5.1 0.61 Diethylenetriamine-MiBK ³⁾ -Diketimine (75% in MiBK) 4.1 0.79 Methylethanolamine 5.3-2-Hexoxyethanol ──────────────────────────────────── (B): Crosslinking agent B1 ──────────────────────────────────── 53.9 2.4 Polyoxybutylene ^{polyisocyanate, Mw~480, NCO-EW 4)} = 240 10.8 - diethylene glycol dimethyl ether 21.4 2.0 BPA 6.4 - toluene 7.5 0.79 dipropylamine ────────────────── ────────────────── (C): Crosslinking agent C1 ───────────────────────── ──────────── 36.1 2.0 Toluylene diisocyanate 24.5 1.0 Butyl glycol 9.4 1.0 Trimethylolpropane 30.0-MiBK

Synthetic resin 2 wt% equivalent component ──────────────────────────────────── 22.6 2.0 BPA -Based diglycidyl ether, EEW ~ 260 20.2-Monoethylene glycol monoethyl ether acetate 0.01-Hydroquinone 14.8 2.0 Tetrahydrophthalic acid 10.0 1.0 Hydroxyethyl methacrylate 15.1 4.0 Toluylene diisocyanate 7.7 2.0 Dimethylethanolamine 9.6-Ethyl Acetate ──────────────────────────────────── (B): Binder B2 ────── ─────────────────────────────── 10.2 8.0 Diglycidyl ether containing BPA as the main component, EEW = 188 14.8 19.2 BPA 0.01 -Triphenylphosphine 14.1-Mi K 48.6 13.0 polyoxypropylene polyisocyanate, Mw~1100, NCO-EW~550 10.7 - diethylene glycol dimethyl ether 1.6 2.7 dimethyl ethanolamine

Synthetic resin 3 wt% equivalent component ──────────────────────────────────── (A) : Binder 3 ──────────────────────────────────── 5.9 9.3 Hexamethylenediamine 7.3 2.4 Dimer fatty acid, Mw ~ 560 1.4 0.45 Linole fatty acid, Mw ~ 280 16.9-Toluol 52.6 10.0 Diglycidyl ether mainly composed of BPA, EEW ~ 485 12.7-Isobutanol 3.2 4.0 Methylethanolamine ────────────── ──────────────────────── (B): Binder ──────────────────── ───────────────── 73.9 0.75 Polyoxyethylene polyisocyanate, Mw-2000, NCO-EW-1000 19.7 -Xylol 4.5 0.39 BPA 1.9 0.15 Diisobutylamine ──────────────────────────────────── (C): Bond Agent C2 ──────────────────────────────────── 47.9 1 Hexamethylene diisocyanate (trimerized) 20.0-MiBK 32.1 1 Dibutylamine

Synthetic resin 4 wt% equivalent component ──────────────────────────────────── (A) : Binder 4 ──────────────────────────────────── 51.2 10.15 Diglycidyl containing BPA as a main component Ether, EEW = 188 17.8 2.7 BPA-ethylene oxide adduct (molar ratio 1: 6), Mw ~ 492 14.8 4.86 BPA 4.4 -MiBK 0.2 -benzyldimethylamine 5.7 0.35 diethylenetriamine-MiBK-diketimine (75% in MiBK) 5.0 1.54 N-Methylethanolamine 0.9-Propylene glycol phenyl ether ──────────────────────────────────── (B) : Binder B4 ──────────────────────────── ───────── 72.4 45.0 Polyoxybutylene polyisocyanate, Mw to 600, MiBK 19.2-MiBK 13.5 15.1 MiBK-Ketoxime 4.8 20.0 Trimethylpropane 0.1 -Dibutyltin laurate ─────────── ────────────────────────── (C): Binder C3 ───────────────── ───────────────────

Synthetic resin 5 wt% equivalent component ──────────────────────────────────── (A) : Binder 4 ──────────────────────────────────── (B): Crosslinking agent B5 ── ────────────────────────────────── 73.3 2.0 Polyoxypropylene polyisocyanate, Mw ~ 2100 12.0-MiBK 8.6 1.0 Ethylhexanol MiBK solution 3.8 1.0 BPA 2.2 -Butyl glycol ──────────────────────────────────── (C ): Crosslinking agent C3 ─────────────────────────────────────

Synthetic resin 6 wt% equivalent component ──────────────────────────────────── (A) : Binder 4 ──────────────────────────────────── (B): Crosslinking agent B6 ── ────────────────────────────────── 49.1 28.0 Polyoxyethylene polyisocyanate, Mw ~ 600 7.0-Toluol 3.7 70.5 Dimethylaminopropanol 1.7 7.05 Ethanol 7.7 16.0 Diglycidyl ether mainly composed of BPA, EEW = 188 0.03-Triphenylphosphine 10.8-MiBK 3.7 12.0 Dibutylamine 1.8 12.0 Paraformaldehyde 11.3 19.2 Bisphenol A ──────── ──────────────────────────── (C): Crosslinking agent 3 ────────────────────────────────────

Synthetic resin 7% by weight equivalent component ──────────────────────────────────── (A) : Binder 5 ──────────────────────────────────── 5.5 2.95 Diethylenetriamine 7.8 1.86 Dimer fatty acid, Mw〜 560 1.5 1.48 Linole fatty acid, Mw ~ 280 1.6-Xylol 40.8 6.0 Diglycidyl ether mainly composed of BPA, EEW ~ 188 11.2 6.75 BPA 2.7-Propylene glycol phenyl ether 0.015-Triphenylphosphine 23.1-Isobutanol 1.185-Butyl glycol 3.7 -Methylethanolamine ──────────────────────────────────── (B): Crosslinking agent B4 ── ─────────────────────────── ──────── (C): Crosslinking agent C3 ──────────────────────────────────── ─

Synthetic Resin 8 (A) Binder 5 (B) Crosslinking Agent B5 (C) Crosslinking Agent C3 Synthetic Resin 9 (A) Binder 5 (B) Crosslinking Agent B6 (C) Crosslinking Agent C3 Comparison Synthetic resin (A) Binder 4 (B) Crosslinking agent C2 Preparation of component (A) Binder 1 A mixture of diglycidyl ether, polycaprolactone diol and xylol in the indicated weight ratios at 210 ° C. under nitrogen. Heated to. Water was then separated by azeotropic distillation. Then it was cooled to 150 ° C. and then a considerable amount of bisphenol A and benzyldimethylamine was added. After maintaining at 150-170 ° C for 1.5 hours, the reaction mixture was allowed to cool to 110 ° C and then diethylenetriamine-methylisobutyldiketimine, methylethanolamine and 2-hexoxyethanol were added to the indicated weight proportions respectively. .. Then, the mixture was stirred at 110 ° C. for about 1 hour.

Binder 2 Diglycidyl ether was dissolved in monoethylene glycol monoethyl ether acetate according to the weight ratios indicated. After adding the corresponding amount of hydroquinone, the half-ester consisting of tetrahydrophthalic acid and ethyl-2-methylpropionate was added to the indicated weight ratio, and then at 105-110 ° C the acid number was lower than 5 mg KOH / g. It was made to react until it became. It was then cooled to 60 ° C. and then mixed with a 70% solution of toluyl diisocyanate semi-masked with dimethylethanolamine in ethyl acetate. The reaction was carried out at 60 to 70 ° C until the NCO value became almost zero.

Binder 3 a) Preparation of amine precursor product 246 g of hexamethylenediamine, 307 g of dimer fatty acid, 59 g of linoleic fatty acid and 31 g of toluol are heated to 190 ° C. and the water of reaction generated (5
7 g) was separated by azeotropic distillation. It was then diluted with 73 g of toluene and then an additional 4.1 g of hexamethylenediamine was added. The amine value of the amine precursor product is 249.
It became mg / g.

B) Preparation of binder 3061 g of bisphenol A in a second stirred vessel
Diglycidyl ether (EEW ~ 48
5) was dissolved in 569 g toluol and 534 g isobutanol. At a temperature of 55 ° C. 135 g of methyl ethanolamine were added. Epoxide equivalent is 835
Was reached, 656 g of the above amine precursor product and 141 g of toluol were added. 2 hours after that
Post-reacted. The binder had a solids content of 70% and a viscosity of 6200 mPas (measured as a 40% solution in propylene glycol phenyl ether at 23 ° C.). The amine value was 91 mg / g.

Binder 4 A mixture of diglycidyl ether, bisphenol A-ethylene oxide adduct, bisphenol A and methyl isobutyl ketone was heated together under nitrogen at 140 ° C. in the indicated weight ratios. The corresponding amount of benzyldimethylamine was added in two portions. At that time, an exothermic reaction occurred and the reaction temperature rose to 180 ° C. At that time, the water was separated by azeotropic distillation. After the water separation was completed, the reaction temperature was kept at 140 ° C. for 2 hours. Then diethylenetriamineisobutyldiketimine as a 75% solution in methylisobutylketone and N-methyleneethanolamine as 3%
Added within 0 minutes. After the post-reaction at 125 to 130 ° C. for 1 hour, a considerable amount of propylene glycol phenyl ether was mixed in with stirring. A resin with a solids content of 93.2% was obtained.

Binder 5 a) Preparation of amine precursor product 5150 g diethylenetriamine, 7250 g dimer fatty acid, 1400 g linole fatty acid and 147.
Slowly add 150 g to 170 g of a mixture of 3 g xylol.
Heated to ° C. Water of reaction (539 g) generated at that time was separated by azeotropic distillation. The precursor product thus produced had an amine number of 464 mg / g and an acid number of 2 mg / g or less at 90% solids content.

B) Preparation of binder In a second stirred vessel, 11280 g of diglycidyl ether based on bisphenol A and epichlorohydrin, 3078 g bisphenol A and 756 g
100 with propylene glycol phenyl ether
Heated to ° C. After adding 4.3 g of triphenylphosphine, heating to 130 ° C. was continued until an epoxide equivalent weight of 435 was reached. After cooling to 100 ° C, 48
58 g isobutanol and 540 g butyl glycol were added. The reaction mixture is then allowed to cool to 55 ° C. and then at this temperature under good external cooling 1019 g
Of methyl ethanolamine was added. After an epoxide equivalent weight of 750 was achieved, 4389 g of the amine precursor product as well as a mixture of 1521 g of isobutanol and 169 g of butyl glycol were added. This was followed by a post reaction for 2 hours. This binder has a solids content of 70% and a viscosity of 4800 mPas (measured at 23 ° C. as a 40% solution in propylene glycol phenyl ether).
Had. The amine value was 145 mg / g.

Preparation of Component B Crosslinking Agent B1 576 g of polyoxybutylene isocyanate of average NCO functionality of 2 was dissolved in 115 g of diethylene glycol dimethyl ether in a stirred flask and warmed to 50 ° C. Add bisphenol A2 to the isocyanate solution.
A solution of 28 g of toluene in 68 g has a reaction temperature of 60 ° C.
It was added dropwise so that it did not exceed. After the end of the addition and at 50 to 60 ° C., the NCO value of the solution is 0.03.
Stirring was continued until it went down to 35. Then, 78.8 g of dipropylamine was added dropwise at 60 ° C. and further stirred until the NCO value dropped to 0. The crosslinker solution thus prepared had a solids content of 83% and a viscosity at 25 ° C. of 3800 mPas.

Crosslinking agent B2 a) Preparation of masking agent 1504 g of diglycidyl ether are heated with 2192 g of bisphenol A and 1.25 g of triphenylphosphine for 2 hours at 150 to 160 ° C., then 20
It was diluted with 87 g of methyl isobutyl ketone.

B) Preparation of the crosslinking agent 7162 g of polyoxypropylene polyisocyanate with an average NCO functionality of 2 were dissolved in 1432 g of diethylene glycol dimethyl ether and then warmed to 50 ° C.
The polyol solution was added dropwise so that the reaction temperature did not exceed 65 ° C. 50-60 ° C after the addition is completed
At, stirring was continued until the NCO value of the solution dropped to 0.0155. Then 240 g of dimethyl ethanolamine was added at 60 ° C. and then at a temperature of 60-75 ° C., N 2
Further stirring was carried out until the CO value fell to 0. The crosslinker solution thus produced had a solids content of 75.5% and a viscosity at 25 ° C. of 2800 mPas.

Crosslinking agent B3 748.8 g of polyoxyethylene polyisocyanate with an average NCO functionality of 2 were dissolved in 150 g of xylol and then warmed to 50 ° C. A solution of 45.6 g of bisphenol A in 20 g of xylol was added dropwise so that the reaction temperature did not exceed 65 ° C. 50-60 after the addition is complete
Stirring was continued at 0 ° C. until the NCO value of the solution dropped to 0.028. Next, 18.7 g of diisobutylamine was added, and the mixture was further stirred at a temperature of 60 to 75 ° C. until the NCO value dropped to 0. The crosslinker solution thus prepared has a solids content of 80% and a solid content of 3 at 25 ° C.
It had a viscosity of 200 mPas.

Crosslinking agent B4 13640 g of polyoxybutylene polyisocyanate having an average NCO functionality of 2 and 2540 of methyl isobutyl ketone.
It was dissolved in g and warmed to 30 ° C. 1 within 3 hours
740 g of methyl isobutyl ketoxime were added dropwise while cooling so that the reaction temperature did not exceed 55 ° C. Then 200 g of methyl isobutyl ketone was added all at once and stirred for 30 minutes at 45 ° C. Then 89
2.5 g of trimethylolpropane were added in 3 equal portions. The reaction temperature was maintained at 40-45 ° C. during the first addition. After stirring for 30 minutes at 40 ° C., a second aliquot was added such that the reaction temperature was between 47 and 50 ° C. During the third addition, no more cooling was applied and the reaction temperature rose to 57-58 ° C. The temperature rose to 95 ° C. after adding 3.65 g of dibutyl tin laurate as catalyst. NCO value is 0
It was further stirred at 70-80 ° C. until the temperature dropped. The crosslinker solution thus produced had a solids content of 85% and a solids content of 25%.
It had a viscosity of 2800 mPas at ° C.

Crosslinking Agent B5 2180 g of polyoxypropylene polyoxyisocyanate having an average NCO functionality of 2 and 3 parts of methyl isobutyl ketone
Dissolved in 60 g and warmed to 45 ° C. 2-ethylhexanol 135 g of methyl isobutyl ketone 120
The solution in g was added slowly such that the reaction temperature did not exceed 60 ° C. After the addition was completed, post-stirring was performed at 50 ° C. for 30 minutes. Then a solution of 114 g of bisphenol A in 65 g of butyl glycol was added. At that time, the reaction temperature is 75 to 7
Raised to 8 ° C. Further, the mixture was stirred at 50 to 60 ° C. until the NCO value dropped to 0. The crosslinker had a solids content of 81.5% and a viscosity of 2500 mPas at 25 ° C.

Crosslinking agent B6 a) Preparation of masking agent See masking agent for crosslinking agent B2.

B) Preparation of the crosslinker 9520 g of polyoxyethylene polyisocyanate with an average NCO functionality of 2 are dissolved in 1350 g of toluene and then 722 g of dimethylaminopropanol and 32
A mixture of 2 g of ethanol was reacted at a reaction temperature of 50 ° C. Next, this reaction solution was added dropwise to the above polyol solution within 90 minutes so that the reaction temperature did not exceed 90 ° C. Then 1551 g of dibutylamine and 361 g of paraformaldehyde were added and then the reaction mixture was stirred for 6 hours at 90-95 ° C. The resulting water of reaction (216 g) was separated by vacuum distillation. The crosslinker solution thus prepared had a solids content of 84% and a viscosity of 3800 mPas at 25 ° C.

Preparation of component (C) Crosslinking agent C1 To 174 g of a mixture of 80/20 isomers of 2,4- and 2,6-toluylene diisocyanate in 54 g of methyl isobutyl ketone, 118 g of butyl under a nitrogen atmosphere. Glycol was added such that the reaction temperature did not exceed 100 ° C. After completion of the addition, post-stirring was performed at 90 to 100 ° C. for 30 minutes. Then 45.7 g of trimethylolpropane were added in 3 portions. At that time, the reaction temperature rose. The reaction was continued until the isocyanate value fell to zero. Then 3
Dilution with 0 g of methyl isobutyl ketone gave a crosslinker solution with a solids content of 80%.

Crosslinking agent C2 5042 g of trimerized hexamethylene diisocyanate were dissolved in 3823 g of methyl isobutyl ketone. With cooling, at 70 ° C. 3881 g of dibutylamine were added dropwise. It was post-stirred until the isocyanate number was almost zero. The product had a solids content of 70%.

Crosslinking agent C3 444.4 g of isoferon diisocyanate 11
It was dissolved in 1.1 g of toluene and then mixed with 0.44 g of dibutyltin laurate. Then, within 1 hour after warming to 60 ° C., 91.2 g of bisphenol A,
A mixture consisting of 53.6 g of trimethylolpropane, 48.3 g of methyl isobutyl ketone and 48.3 g of toluene was added dropwise. After another 2 hours, the isocyanate value was 10.5%. And 258g
Was added dropwise so that the reaction temperature did not exceed 80 ° C. After the reaction is completed, 155.2
Diluted with g toluene to 70% solids content.

Preparation of Synthetic Resin Dispersion Synthetic Resin Dispersion 1 1145 g of Binder 1 were thoroughly mixed with 310.9 g of acetic acid. The mixture is gradually added to 1743 g of VE ⁵⁾ −
Mixed with water. The volatile solvent was then removed by azeotropic distillation in vacuo at 40 ° C. Then add the dispersion to V
Diluted with E-water to a solids content of 34%.

Synthetic Resin Dispersion 2 1100 g of self-crosslinking binder 2 were thoroughly mixed with 997 g of crosslinker 2 and 65.3 g of acetic acid and then gradually mixed with 1830 g of VE-water. It was Volatile solvents were removed by azeotropic distillation at 40 ° C. The dispersion was then diluted with VE-water to a solids content of 37.5%.

Synthetic Resin Dispersions 3-9 General Working Guidelines The amounts of binder, crosslinker B and crosslinker C listed in Table 1 were thoroughly mixed with 16 g of acetic acid. The mixture was then slowly mixed with 3121 g of water, then the volatile solvents were removed by azeotropic distillation at 40 ° C. in vacuo. The dispersion thus obtained had a solids content of 24.5%.

Table 1 Synthetic Resin Binder Crosslinking Agent Crosslinking Agent Dispersion No. No. / [G] No. / [G] No. / [G] ──────────────────────────────────── 3 3/511 B3 / 391 C2 / 298 4 4 / 420.8 B4 / 160.2 C3 / 194.5 5 5 / 420.8 B5 / 167.2 C3 / 194.5 6 4 / 420.8 B6 / 162.2 C3 / 194.5 75 /429.6 B4 / 160.2 C3 / 194.5 8 5 / 429.6 B5 / 167.2 C3 / 194.5 9 5 / 429.6 B6 / 162.2 C3 / 194.5

Comparative synthetic resin (A): Binder 4 (B): Crosslinking agent C2 Comparative synthetic resin dispersion 43% binder 4 and 20% crosslinking agent C2 Component (D) Pigment preparation bisphenol 640 g of diglycidyl ether mainly composed of A and epichlorohydrin and having an epoxide equivalent of 485
And diglycidyl ether 16 having an epoxide equivalent of 188 and containing bisphenol A and epichlorohydrin as main components
0 g was mixed at 100 ° C. 452g in the second container
Of hexamethylenediamine are added in advance and heated to 100 ° C., and then 720 g of the above epoxy resin mixture is added to
Added in time. At that time, it had to be cooled lightly in order to keep the temperature at 100 ° C. After another 30 minutes, excess hexamethylenediamine was removed under reduced pressure and temperature rise. At that time, at a temperature of 205 ° C. and 30
A pressure of mbar was reached. Then 57.6 g stearic acid, 172.7 g dimer fatty acid and 115 g xylol were added. Then, the water of reaction formed within 90 minutes was removed by azeotropic distillation at 175 to 180 ° C. Then 58
It was diluted with g butyl glycol and 322 g isobutanol. The product had a solids content of 70% and a viscosity of 2240 m measured at 75 ° C. by a Platekegel viscometer.
Had a Pas.

110 g of the surface-active resin thus obtained are placed in a ball mill in an amount of 36 g ethylene glycol monobutyl ether, 3 g acetic acid, 170 g titanium oxide, 18 g lead silicate, 4.5 g carbon black and 170 g. It was ground with water to a particle size of 7 μm or less.

Electrophoretic lacquer coating baths Pigment preparations for the synthetic resin dispersions 1 to 9 according to the invention and the comparison dispersions, respectively, for component (A) (binder) component (D) (pigment preparation). A weight ratio of 2: 1 was always added. The bath solids were always adjusted to 20% with water. At that time, the bath volume always reached 5 liters. The electrophoretic lacquer bath was stirred for 7 days at 30 ° C. 150 ~ 150 mm on a sample plate made of zinc-phosphoric acid treated steel plate of size 190 x 150 mm connected to the cathode
22 ~ at a bath temperature of 27 ° C within 2 minutes at a voltage of 500V.
A resin film having a thickness of 24 μm was deposited. The resin coating was then baked at 165 ° C within 20 minutes.

The bath composition and test results are shown in Table 2.

[0080]

[Table 1]

ET: Erichsen extrusion test RI: Backside impact, impact extrusion test: ASTM D279
Measurement with a Gardner Mandrel Impact Tester according to 4.

SST: 480-hour salt spray test of bare strip, penetration value (mm) according to DIN 50021.

KWT: Climate change test, 10 cycle permeation value (mm), VDA 621-415.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09D 175/04 PHP 8620-4J PHV 8620-4J (72) Inventor Dieter, Foul Germany, 6702, Bert, Dürkheim, Goethestraße, 4 (72) Inventor Gerhard, Hoffmann, Federal Republic of Germany, 6701, Otterstadt, Papelstraße, 22

Claims (10)

[Claims] 1. A bridge consisting of, as essential constituents, A) a group of polymerization, polyaddition or polycondensation products having reactive centers in the form of hydroxyl groups, thio groups, primary or secondary amino groups. A bridging binder, and B) a cross-linking agent having at least one polyoxyalkylene polyisocyanate as a main component, and C) γ ₁ ) _{one of} polyvalent isocyanates different from (B), or γ ₂ ) Organic compound which reacts by forming amide with free amino group of component (A) at high temperature, or γ ₃ ) Organic compound which reacts by transesterification with hydroxyl group of component (A) at high temperature, or γ ₄ ) Phenol A synthetic resin containing a Mannich base or a mixture of two or more binders (γ ₁ ) to (γ ₄ ) as a main component, and one of binders different from (B). 2. A crosslinkable binder consisting of the group of polymerisation, polyaddition or polycondensation products having reactive centers in the form of hydroxyl groups, thio groups, primary or secondary amino groups, a ₁ ) polyester, or a ₂₎ an alkyd resin or a _3,) polyethers or a ₄₎ a polyacrylate or a ₅₎ a polyurethane or a ₆₎ an epoxide resin, or from (a ₁₎ to (a _5),,, The synthetic resin according to claim 1, which is a mixture of two or more binders. 3. Essentially, A) 50 to 95% by weight of α ₁ ) polyhydric phenol having an average molecular weight Mw of 200 to 5,000 as a main component and, on average, 1.5 to 3.0 per molecule.
An epoxide group-containing diglycidyl ether, and α ₂ ) α _2.1 ) primary C ₂ -C ₂₀ -alkyldiamine, α _2.2 ) secondary di-C ₁ -C ₂₀ -alkylmonoamine, α _2.3 ) C ₁ -C ₂₀ - alkyl -C ₁ -C ₂₀ - alkanolamines, alpha _2.4) polyoxyalkylene polyamine, alpha _2.5) multivalent polyolefin amines, α _2.6) C ₁ including the secondary and masked primary amino group - A crosslinkable binder based on an epoxide resin obtained from at least one amine of the group C ₂₀ -alkylamines, and B) 5 to 50% by weight of β ₁ ) polyoxyethylene polyisocyanate, β ₂₎ polyoxypropylene polyisocyanate, beta ₃₎ polyoxybutylene polyisocyanate, at least one polyoxyalkylene Lee from the group of Crosslinking agent mainly composed of cyanate, C) 5 to 50 wt.%, Gamma ₁₎ free of (B) is different from one of a polyvalent isocyanate or gamma ₂₎ component at elevated temperature, (A) Amino An organic compound that reacts by forming an amide with a group, or γ ₃ ) an organic compound that reacts by transesterification with the hydroxyl group of component (A) at high temperature, or γ ₄ ) a phenolic Mannich base, or (γ ₁ ) One or more cross-linking agents based on (B) different from (B), based on a mixture of two or several binders up to (γ ₄ ), D) one or more pigments and one surface-active resin A synthetic resin according to claim 1 or 2, comprising 0 to 30% by weight of a pigment preparation, and E) 0 to 10% by weight of an additive. 4. The synthetic resin according to claim 1, wherein the polyoxyalkylene polyisocyanate is masked. 5. The polyoxyalkylene polyisocyanate is masked with at least one masking agent selected from the group consisting of β ₁ ) ketoxime, β ₂ ) polyhydric alcohols, β ₃ ) aromatic polyols. 4. The synthetic resin according to any one of 4 to 4. 6. The synthetic resin according to claim 1, wherein the ketoxime is methylisobutylketoxime. 7. An aqueous dispersion containing the synthetic resin according to claim 1 in an amount of 10 to 40% by weight. 8. A method for producing an aqueous dispersion according to claim 7, wherein before mixing all the synthetic resin components according to any one of claims 1 to 6, the components (A) and ( A production method characterized in that each time B) is protonated, then separated, and dispersed in advance. 9. Use of the aqueous dispersion according to claim 7 in an electrophoretic lacquer bath. 10. Article coated with cathodic electrophoretic lacquer, obtainable using the aqueous dispersion according to claim 7.